JPS62115437A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having satisfactory dimensional stability, enabling the hardening of each separate specified layer and nearly independent of tailing trouble caused during production by incorporating latex having hydrophilic groups fixed on the surface and a polymer hardening agent into a photographic constituent layer. CONSTITUTION:Latex having hydrophilic groups fixed on the surface and a polymer hardening agent are incorporated into a photographic constituent layer on a support. The latex is obtd. by converting latex into protective colloid with a polymer having hydrophilic groups or by allowing a compound having a hydrophilic group to take part in a latex forming reaction so that the compound is distributed on the surfaces of latex particles. The hydrophilic groups contribute toward stabilizing the latex. The polymer hardening agent is a polymer having functional groups which can cause a cross-linking reaction with gelatin or a polymer having functional groups which can cause a cross-linking reaction with gelatin through a hardening agent. The preferred polymer hardening agent is a (co)polymer of a vinyl monomer.

Description

[Detailed Description of the Invention] Field of Application in the fM Industry] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has good dimensional stability, can be hardened layer by layer, and has the following features: The present invention relates to a silver halide photographic material in which failures occurring during manufacturing, particularly trailing failures occurring during coating, are improved.

[Background of the Invention] A silver halide photographic material having a hydrophilic colloid layer prevents the hydrophilic colloid from being eluted during the development process, moderately suppresses swelling, and resists friction and compression during rough handling. Therefore, in general, hardeners are used to fix Fp! It is imitated. Hardeners commonly used have good diffusibility in the existing aqueous colloid layer, and for example, by adding the hardener to the coating solution for the daylight layer, it is possible to simultaneously
After one coat of J coating, the hardening agent diffuses until the drying process of the photosensitive material is completed, and the degree of hardening within the photosensitive material becomes uniform or continuous.

In recent years, the design of silver halide photographic materials has become more sophisticated, and in sensitive materials consisting of two or more layers, it has become necessary to independently control the degree of hardening of the hydrophilic colloid layer for each layer. . It is known that a polymer hardener is used as a means for achieving such hardening of each coated layer.

On the other hand, in order to reduce the gelatin content and improve the physical properties of the film, such as dimensional stability before and after development, dimensional stability against moist heat, flexibility, pressure resistance, and drying properties, latex was combined with gelatin. It is generally well known that silver halide is used as a binder for photographic materials.

Therefore, the use of latex can also be considered in sensitive materials that are hardened with polymeric hardeners. For example, JP-A-59
In No. 12137, a polymeric hardener and latex are contained in a non-photosensitive upper layer to improve reticulation.

However, when such a polymer hardener and some latex are added to a coating solution for a hydrophilic colloid layer mainly composed of gelatin, fine lumps are formed, which causes trailing failures during coating and reduces commercial value. It has decreased significantly.

Furthermore, such tailing failures occur not only when the polymeric hardener and latex are present in the same hydrophilic colloid layer, but also when they are present in separate adjacent layers. For example, when a silver halide emulsion layer containing latex and a protective layer containing a polymeric hardener are simultaneously coated on a support in multiple layers, if the amount of latex increases, the problem of trailing still occurs. For this reason, there is little latex]
Therefore, a silver halide photographic material with sufficiently good dimensional stability could not be obtained.

[Object of the Invention] Accordingly, the object of the present invention is to achieve good dimensional stability and rJJ! It is an object of the present invention to provide a silver halide photographic material which can be formed into a film and which has improved tailing defects that occur during production.

[Structure of the Invention] The object of the present invention was achieved by including a latex having a hydrophilic group fixed on the surface and a polymer hardening agent in a photographic constituent layer on a support.

[Specific Structure of the Invention 1 In the present invention, the term "hydrophilic groups fixed in the margin below the surface of latex" refers to a state in which the latex is made into a protective colloid by a polymer having hydrophilic groups, or a hydrophilic It refers to a state in which a compound having a group participates in the latex formation reaction and is attached to the surface of the latex particles, both of which contribute to the stabilization of the latex.

The state in which latex is converted into a protective colloid by a polymer having a hydrophilic group is a state in which the polymer having a hydrophilic group is strongly adsorbed and immobilized on the surface of the latex. In addition, the state in which a compound having a hydrophilic group participates in the latex formation reaction and is placed on the latex particle surface refers to a state in which a compound having a hydrophilic group (e.g., a polymer having a hydrophilic group, a hydrophilic compound in the molecular structure) There are polymers that have both a functional group and an ethylenic double bond, and compounds that have a hydrophilic group and a group that allows easy chain transfer of radicals in the molecular structure, etc.) that participate in the latex formation reaction, and the A part of the powder is covalently combined with the latex and is fixed in the state 4 and placed on the surface of the latex powder.

Polymers having hydrophilic groups include synthetic water-soluble polymers and natural water-soluble polymers, both of which can be preferably used in the present invention. Among these, synthetic water-soluble polymers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures. Examples of nonionic groups include ether groups, ethylene oxide groups, hydroxyl groups, etc., and examples of anionic groups include sulfonic acid groups or salts thereof, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, etc. can be given. In addition, as a natural water-soluble polymer, there are
Examples include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group.

As the polymer having a hydrophilic group, in both synthetic water-soluble polymers and natural water-soluble polymers, those having anionic groups, and those having nonionic groups and anionic groups can be preferably used. In the present invention, a polymer having a parent wood group is defined as
It is sufficient to dissolve O.osg or more per 0g, preferably 0.01g or more.

Examples of synthetic water-soluble polymers include those containing 10 to 100 mol % of repeating units represented by the following general formula rP in one polymer molecule.

General formula [P] In the formula, R1 is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent, such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.) ), halogen atom (e.g. chlorine atom) or -CH2
Represents C00M, L bar CON H-1-NHC
O-1-COO-1-〇C0-1-〇〇- or 10-
, J is an alkylene group, preferably having 1 carbon atom
~10 alkylene groups (including those with the right substituents).

For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.), arylene FS (including those having substituents).

For example, phenylene group, etc.), or →CH2CH20- term 1 → CH2 power mouth (m is an integer of O to 40, n is an integer of O to 4) -CR
2, represents a hydrogen atom or R3, preferably -3
03M is most preferred. M represents a hydrogen atom or a cation, R2 is an alkyl group having 1 to 4 carbon atoms (VIJ
(eg, methyl group, ethyl group, propyl group, butyl group, etc.), and R3, Rs, Rs, Rs, R7 and R8
is an alkyl group having 1 to 20 carbon atoms (e.g. methyl group,
ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.), X represents an anion, and p and q each represent O or 1.

Next, specific examples of the synthetic water-soluble polymer of general formula [P] will be given.

Margin below 5P-1 number average molecular weight j・1゜ P-2 10CH2-CH7 NH26,200 P-3 p-s 5P-6 SP-7 P-8 CH.

P-10 CH3 P-11 SP-1,2 P-14 →CH2-CH soup τ 0COCH34,o00 P-15 SP 17 CH.

5P-1,8 P-19 P-20 9,000 P-21 P-22 P-23 P-24 SP-25 CH3 ■ P-28 2,100 P-31 S 03 N a 163.000 P-33 P-34 SP-35CH3 P-36 uuh CH3 Nawate CH.

5P-445050 (C1-12-CH±
4.900COOCH2CH)SO)Na SP-4550So -+CH-CH-)-2
, 800 COOHC0OH P-47 SQ Co Na l Q, 5 0 0 P-48 P-49 P-50 15,600 The synthetic water-soluble polymer of the present invention can be easily synthesized by various methods such as solution polymerization, bulk 112 polymerization, 22 polymerization, etc. It can be synthesized into

For example, melt? i. In polymerization, a mixture of heptamine at an appropriate concentration (usually 40% by weight or less based on the solvent,
Preferably a mixture of 10 to 25% by weight) and a polymerization initiator (
For example, benzoyl peroxide, azobisisobutyronitrile, ammonium periaate, etc.) at an appropriate temperature (
For example, the copolymerization reaction is carried out by heating to 40 to 120°C, preferably 50 to 100°C. Thereafter, the reaction mixture is poured into a medium that does not dissolve the produced water-soluble polymer, the product is precipitated, and the unreacted compound a is separated and removed by drying. The intermolecular distance of the water-soluble polymer of the present invention is preferably 1,000 to 1.000.000°, and preferably 2.000 to 200.000°.

J3, the intermolecular distance of the water-soluble polymer of the present invention is expressed as a number average intermolecular, and the constant is determined in terms of standard polybrene using Toyoso Co., Ltd. Gel Vermeation Chromatography HLC-802A. .

Synthesis Example 1 (Exemplary Compound 5P-18) 3-sulfopropyl acrylate potassium salt 50(1(
0.22 mol), 4.4'-azobis(4-cyanovalein iM)3. Three Oq and 200 iR of degassed water were placed in a flask, and this flood mixture was reacted at 80° C. for 8 hours. After the reaction was completed, the reaction solution was poured into a large amount of acetone while stirring vigorously to precipitate the reaction product. Then, the precipitate was filtered, washed with acetone, and washed in air for 6 hours.
It was dried at 0°C to obtain polymer 5P-18 of the present invention. Yield: 45g (90% of theoretical yield), number average molecule...
Mn=4,300.

Synthesis Example 2 (Exemplary Compound 5P-21> Styrene 52 (1 (0.50 mol), acrylic acid 36Q
(0.50 mol), 5.0 g of 4,4'-azobis(4-cyanovalein), and 50 g of degassed ethanol.
0iN was placed in a flask, and the mixture was reacted under two streams for 8 hours. After the reaction is complete, while stirring vigorously,
After pouring into a large amount of acetone, the same treatment as in Synthesis Example 1 was carried out to obtain Polymer 5P-21 of the present invention. Mouth is 80g (91% of theoretical intake), number average molecular weight Mn
= 2,600.

Synthesis Example 3 (Exemplary Compound 5P-42) Hydroxyethyl methacrylate 52 g (0.4θ mol), sodium 2-acrylamido-2-methylpropanesulfonate 137 g (0.60 mol), 4.4'-azobis(4-cyazubarein) acid)5. Oa and degassed water-ethanol = 80/20 v% solution 500
Put 3 M+2 into a flask and heat this mixture at 80℃.
The reaction was allowed to proceed for 0 hours. After the reaction is complete, while stirring vigorously,
The reaction solution was poured into a large amount of acetone to precipitate the reaction product.

The precipitate was then filtered, washed with acetone, and dried in air at 60 DEG C., giving the polymer 5P-42 of the present invention a blue color. Yield is 1
number average molecular ωMn = aog (95% of theoretical yield)
It was 5,300.

Natural water-soluble polymers are described in detail in the Comprehensive Technical Information Collection of Water-Soluble Polymer Water-Dispersible Resins (U-Eng Development Center Publishing Department), but include lignin, starch, pullulan, cellulose, alginic acid, dextran, and dextrin. , guar gum, gum arabic, glycogen, laminaran,
Lignin, nigeran, etc., and derivatives thereof are preferred.

As derivatives of natural water-soluble polymers, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated derivatives, and salts thereof are particularly preferred.

In the present invention, two or more natural water-soluble polymers may be used in combination.

Furthermore, among natural water-soluble polymers, glucose polymers and their derivatives are preferable, and among glucose polymers and their derivatives, starch, glycogen, cellulose, lignin, dextran, nigeran, etc. are preferable, and dextran and its derivatives are particularly preferable. Training instructors are preferred.

Textran is a polymer of α-1,6-linked D-glucose, and is generally produced by culturing dextran-producing bacteria in the presence of saccharides (9). It can be obtained by reacting dextran sucrase isolated from a culture solution with saccharides.In addition, these native dextrans can be lowered to a desired molecular weight by partial decomposition polymerization using acid or alkaline enzymes, and the intrinsic viscosity can be reduced to a desired value. 0.
03 to 2.5 can also be obtained.

In addition, dextran modified products include dextran sulfate ester, in which a sulfate group exists in the dextran molecule as an ester bond, carboxyalkyl dextran, in which the carboxyalkyl group exists in the dextran molecule as an ether bond, and Carboxyalkyldextran sulfate esters in which the sulfate group is an ester bond and the carboxyalkyl group is an ether bond, and salts thereof, dextran phosphate esters in which 1 g of phosphorus is present in the ester bond in the dextran molecule, and salts thereof, dextran molecules Examples include hydroxyalkyldextran into which a hydroxyalkyl group is introduced.

The use of these dextrans in silver halide photographic materials is disclosed in Japanese Patent Publication No. 35-11989, U.S. Pat. No. 40149, 46-
As described in No. 31192, these dextrans' are incorporated directly into silver halide emulsions or gelatin layers to improve the covering power, maximum density, and contrast of developed silver images. Improving.

Methods for producing these dextrans and their derivatives are described in detail in these patents.

Among these dextran and its modified products, from the viewpoint of latex dispersion stability, dextran sulfate ester, carboxyalkyl dextran sulfate ester, and dextran phosphate ester, in which anionic groups have been introduced, are particularly preferred. Sulfuric acid esters are most preferred.

These dextran modified products can be synthesized by using the above-mentioned dextran as a raw material, and in the presence of a hydrochloric acid-containing solvent such as pyridine or formamide, a sulfating agent such as chlorosulfuric acid is avoided to obtain dextran sulfate ester. can. .

Furthermore, carboxyalkyl such as monochlorocarboxylic acid Quitran sulfate is obtained.

Alternatively, using dextran as a raw material, it is possible to react with a carboxyalkylating agent such as monochlorocarboxylic acid in an alkaline environment to produce carboxyalkyldextran (q). By reacting with a sulfurizing agent such as chlorosulfonic acid, a carboxyalkyl dextran ester can be obtained.Additionally, oxides of alkali metals such as sodium and potassium, and oxides of alkaline earths such as calcium and magnesium are added. If oxides, hydroxides, ammonia, etc. are reacted, each will produce dextate 52
A 14M ester, a salt of a carboxyalkyl sulfate ester, is obtained.

Since dextran has three hydroxyl groups that can be substituted per anhydroglucose unit, it is theoretically possible to substitute sulfuric ester groups and carboxyalkyl groups with an excessive degree of substitution of up to 3, but the reaction conditions must be carefully selected. It is possible to produce products with any degree of substitution within the range of degree of substitution of 3 or less.

However, the sum of the degrees of substitution of the I'fIi ester group and carboxyalkyl cannot exceed 3.

The carboxyalkyl dextran, dextran sulfate, and carboxyalkyl dextran sulfate ester produced in this way can be produced in many types by varying the intrinsic viscosity of the raw material dextran and the degree of sulfate ester substitution and carboxyalkyl substitution degree of the product. I can do it.

The polymer having a hydrophilic group and an ethylenic double bond in its molecular structure is preferably a polymer containing a compound represented by the following general formula [■][V[ ] or [■] as a main component.

Here, examples of the hydrophilic group include the same ones as those mentioned for the polymer having a hydrophilic group.

General formula [Vl] [wherein, R1 is a divalent organic group, Ml is a hydrogen atom or 7
nl represents a valent cation, nl is 30 to 95 mol%, nl
represents 70 to 5 mol%. 1 General formula [■] ■ CH 2 COOH3 CH 2 CONCH 2 CH2 SO3 H 5^
, [wherein R2 is a hydrogen atom or an alkyl group, M2,
M3, Mq J3 and MS each represent a hydrogen atom or a monovalent cabone, n3 is 30 to 95%,
n4 is 70 to O mol%, n5 is 70-O [Representing Le 96 M. However, n,, -+n5 is 70 to 5 mol%.

] General formula [■1 Soy sauce [In the formula, R3 is a hydrogen atom or an alkyl group, MS, M
7, MA and MS each represent a hydrogen atom or a monovalent cab-one, n6 represents 30 to 70 mol%, 01 represents 5 to 50 mol%, and n8 represents 70 to 5 mol%. However, n7+nB is 70 to 30 mol%. 1 Next, general formulas [VI], [■], and [■] will be specifically explained. The divalent organic group represented by R1 is ethylene, trimethylene, tetramethylene, hexamethylene, propenylene, and 3.

Divalent residues of aliphatic hydrocarbons such as 6-thioxaoctane-1,8-diyl, 2,2-dimethyltrimethylene, propylene, 1,4-cyclohexylene, 1. tl, 2-dichloroethylene, 2-chlorotrimethylene, 2-bromotrimethylene, 1-cyanomethylethylene, 1-chloromethylethylene, 1-methoxymethylethylene, 1-phenoxyethylene, and other halogen atoms, cyano groups, alkyl Divalent residue of aliphatic hydrocarbon substituted with oxy group, aryloxy group, etc., or 1,4-phenylene, 1.3
-t-rylene, 2-chloro-1,4-phenylene, 2-
Cyano-1,4-phenylene, 2-methoxy-1,5-
Divalent residues of aromatic hydrocarbons such as phenylene or divalent residues of aromatic hydrocarbons substituted with halogen atoms, cyano groups, alkyloxy groups, etc., or 1.1'-(1,
4-phenylene)dimethyl, 2.2'-(2-chloro-1,4-7enylene)diethyl, 2.2'-(2-
211 of an aliphatic hydrocarbon bonded to a divalent residue of an aliphatic hydrocarbon such as cyano-1,4-phenylene) diethyl or an aryl group substituted with a halogen atom, a cyan group, etc.
Five residues are mentioned.

Ml, M2, M3, M4 and M5 represent a hydrogen atom or a monovalent cation of an alkali metal such as lithium, sodium or potassium or an ammonium cation. As the polymer having a hydrophilic group and an ethylenic double bond in its molecular structure, a compound represented by the general formula [VI] is preferred.

Next, typical examples of the polymer of the present invention will be exemplified below, but the invention is not limited thereto.

The following margin (however, n+: nz = = 50 mol: 50 molar coefficient, number average molecule t (Mn) = approximately 10.000) 5 mol Hiro M71 =
(approximately 20,000) (However, nl: n2 = 75 mol: 25 mol, Mn
= approximately 2o, ooO) 03Na (However, r++: n2 = 50 molar ratio = 50 molar ratio, M
n = approximately 25,000) D-7I: (However, n+: n2 = 3Q mol% = 70 mol ratio,
Polymer Mn=about 21,000) (However, nl: 1z==3Q mol%=70 mol ratio,
15,000 M bars CH2C0NHCH2CH25O3Na (1 time, n+
:n2=50 mol%: 50 mol ratio, Mn=D2.000
) CHCOONa CH2C (J Oi'Ja CHCOONa CH2CONHCH2CH2S 03 Na (however, n
l: nl: n3=80 molar ratio: 10 molar ratio: 10
molar ratio, M = approximately 6,000) CHCOONa CH2CQNCH2CH2SO3Na Hs (hence, n+: nz = 95 mol%: 5 mol ratio, Mn
= approximately 3,000) (However, n+: nz = 5Q mol%: 50 mol ratio, J = approximately 10,000) CH3 (However, ru: 112: n3 = 50 mol%
: 45%le% : 5mol%, Mrt-approx. 15,00
0) The synthesis method of these polymers is described in Japanese Patent Application Laid-Open No. 55-50240.
listed in the number.

Examples of the hydrophilic group of a compound having a hydrophilic group and a group to which a radical is easily chain-transferred in its molecular structure include those similar to those described for the polymer having a hydrophilic group.

Furthermore, a group in which radicals are easily chain-transferred refers to a group in which an active point is easily transferred, such as a polymerization initiator radical generated when polymerizing a polymerizable unsaturated compound, or a polymeric acid long-chain radical, I can do what I like. In the above groups, R is a hydrogen atom or an alkyl group, R' is an alkyl group or a carbonyl group, Rn is a hydrogen atom or an alkyl group or a carbonyl group, and X is a hydrogen atom or a halogen atom.

The fact that these groups are easily chain-transferable was reported in "Copolymerization-2-", Polymer Science Society, November 1976, Gekko J Te, 38.
It is written on page 1. And these If7) middle T
--3H1-NHR', -CH23r are more preferred, and -8H is most preferred.

Groups that are susceptible to chain transfer may have a negative value of the hydrophilic parameter π. In this case, it is preferable that the group that is susceptible to chain transfer and the hydrophilic group are not the same. Further, the number of hydrophilic groups may be at least 1 per molecule, preferably 1 to 4 per molecule, and more preferably 1 to 2 per molecule. When the number of hydrophilic groups is two or more in one molecule, the hydrophilic groups may or may not be the same.

In addition, the number of groups that are easily chain-transferred in one molecule should be at least 1, preferably 1 to 3, and 1 to 2.
More preferably.

The compound having at least one hydrophilic group and one group in each molecule that is susceptible to chain transfer of radicals is preferably one represented by the general formula [T].

General formula [T] (Heta, J→B) However, in general formula [T], A is a hydrophilic group, and the details are as described above. B is a group in which radicals are easily chain-transferred, and the details are as described above. m is an integer of 1 or more, preferably 1 to 4, more preferably 1.2
It is. n is an integer of 1 or more, preferably 1 to 3,
More preferably, it is 1. J may be anything as long as A and B are chemically bonded via J, but it may be an alkyl group including those with substituents, a phenylene group including those with direct substituents, or a heterocycle including those with substituents. Mention may be made of groups as well as combinations thereof.

As a specific example of a compound having a hydrophilic group and a group that is likely to be linked with a radical in its molecular structure, for example, the following compound T-1
-Compound T-113 can be mentioned.

The following margins are complete - I H (30C-CH, -5HT-2) (○O
(, -CH, -CH2-8) (HOH Below margin τ-1x HO-CHx =, 0H-CH2-NH-
Co-OHs -5ELH T-12HOOC-CFlz -NH-Co-CH2-
3H〇-4T-14(HOC2H<)21N-u-CH2-8H-15)&N-CzH+-3HT-20HOOC-CH
-CH, -3HH28H N)h C
Hz -CHsT-28CH.

)(0(Ic-C-CH2-3H Nl(.

T-3106H, T-22 Ht-, +0e-C-3H TOE000-C:2F (<-
3oZooC)T, -CH2-5HC,6H.

0T (2-CH30H T-35FaO3F-(OHz)z -SHτ-36C
4-13-C-C15-EJHT-39) 400C-C
Mountain-CH-3HT-40N203S-(C1%)2-8
H [C6H.

T-<l Na0)S-(CH2)3-3HT-
42Na○sS-(CH2)a-8HC)13
CHff CH-J 7-49 CH3I HOCJO-C)i? -C-8H CH3 CH2 0iNHz H○tsu CNH: S (J, Nicho-62-63 OOC SH T-74EOOC (CHri4 CHBHl 1 (f9-CH!-Carasu HOOC) I 04H.

C,H.

T-97BrCH2CH2C0OHT-98Br(CH
,), CtJ+-99CH3(CH2)3CHBrCO
OHryo-100Br (cHL) ICOOHT-401B
r(CH2), OHT-102Br(CH2)tocO
OHT-1030AICHχC Old, T-104
Cl(CH2)40H1-105(J(CB,),00
0HT-106CICH, (CH, enter C00HT-10
7CI(OH1)4COOHT-2080g8tC)1
2NHC)(2CE20)(CH-CH.

Summer 0OH T-111H8+c day, C1(,Cka5OxH)(0
0C-C-CHRr3! (CH.

The following margins These compounds (1) to (113) are all known compounds, and some of them are added to the developer as a dark coloring and sludge generation prevention agent as described in JP-A-54-133331. is used.

In the present invention, methods for fixing a polymer having a hydrophilic group on the surface of latex include adding it to the polymerization system as a dispersant before polymerization when producing latex by emulsion polymerization, and producing latex without a dispersant. There is a way to add it again. In the method of adding before polymerization, the added polymer with hydrophilic groups undergoes graft polymerization, is incorporated into the latex particles and is fixed, and the end of the polymer with hydrophilic groups is exposed on the surface of the latex particles. becomes. In addition, in the polymerization addition method, when a polymer having a hydrophilic group is added to latex, it is heated, stirred at 60° C. or higher for 1 hour or more, and then cooled before use. Then, the polymer having hydrophilic groups, which was merely mixed, is strongly adsorbed to the latex surface and becomes immobilized.

This is due to the fact that when the viscosity of the system is measured, the viscosity decreases after heating and cooling u1, which indicates that the amount of polymer having free hydrophilic groups has decreased. In the present invention, it is more preferable to add it before polymerization.

The latex of the present invention can be easily produced by various methods. For example, there are emulsion polymerization methods, methods of redispersing polymers obtained by solution polymerization, bulk polymerization, etc., but emulsion polymerization methods are preferred.

In the emulsion polymerization method, water is used as a dispersion medium, and the ratio of 10 to 5
About 30 to 100°C, preferably 60 to 90°C, using 0% by weight of monomer, a polymerization initiator of 5% by weight of O, OS, and 0.1 to 20% by weight of D based on the monomer.
It is obtained by polymerizing under stirring for 3 to 8 hours.

Monomer concentration, initiator inlet, reaction temperature, time, etc. can be varied widely and easily.

The polymer having a hydrophilic group used in the latex of the present invention is preferably used in an amount of 0.1 to 20% by weight, more preferably 1 to 15% by weight, based on the monomer Q.

In the present invention, as a method for fixing a polymer having a hydrophilic group and an ethylenic double bond in its molecular structure to the surface of latex, when producing latex by emulsion polymerization, it is added as a dispersant to the polymerization system before polymerization. There is a way to add it.

In this case, the added polymer having a hydrophilic group and an ethylenic double bond in its molecular structure undergoes graft polymerization and is incorporated into the latex particles. It is considered that the terminal end of the polymer having the above properties is exposed on the surface of the latex particle.

In the emulsion polymerization method, water is used as a dispersion medium, and the ratio of 10 to 5
Using 0% by weight of monomer, 0.05 to 5% by weight of polymerization initiator to the monomer, and 0.1 to 20% by weight of a polymer having a hydrophilic group and an ethylenic double bond in the molecular structure. , at about 30-100°C, preferably 60-90°C.
Obtained by polymerization under stirring for ~8 hours. The monomer concentration, initiator m, reaction temperature, time, etc. can be varied widely and easily.

The polymer having a hydrophilic group and an ethylenic double bond in its molecular structure used in the latex of the present invention is preferably used in an amount of 0.1 to 20% by weight, more preferably It is 1 to 15% by weight.

In the present invention, a method for immobilizing a compound having a hydrophilic group and a group to which radicals are easily chain-transferred onto the surface of latex is to immobilize a compound having a hydrophilic group and a group to which radicals can easily chain-transfer in the presence of a compound having a hydrophilic group and a group to which radicals can easily chain-transfer. There is a method of polymerizing saturated compounds. By this method, a polymerizable unsaturated compound is bonded to the radical and a compound having a group that is easily chain-transferred via a group that is easily chain-transferred, thereby obtaining a polymer in which a hydrophilic group is introduced into the molecule.

Compounds having a hydrophilic group and a group to which radicals are easily chain-transferred in one molecule are used alone or in combination of two or more, and the blend m is vinyl 7-mer-10 that forms latex.
0ffi 0.0001-05% by weight based on f2i part
is preferable, more preferably 0.001 to 0.2% by weight
It is.

A surfactant is normally used as a dispersant during latex production, but it is preferable not to use it in the present invention. When used, dispersion stability often deteriorates.

Examples of initiators include water-soluble peroxide vIJ (e.g., potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (
For example, 2.2'-azobis-(2-amidinopropane)
-hydrochloride, etc.).

Examples of the ethylenic monomer compounds forming the latex of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric acid diesters,
One or a combination of two or more selected from acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids. Mention may be made of monomer compounds.

More specifically, these monomer compounds are as follows:
Examples of acrylic esters include methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, t
ert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-pro11-
Ethyl acrylate, 4-chlorobutyl acrylate,
Cyanoethyl acrylate, 2-acetoxyethyl methacrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-
Chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypenglu acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxy ethyl acrylate,
3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate,
2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-
Examples include bromo-2-methoxyethyl acrylate, 1<1>-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl acrylate, lobutyl methacrylate, inbutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, and cyclohexyl. Methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate,
Sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl Methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate , 2-ethoxy nibble methacrylate, 2-iso-proboxyethyl methacrylate,
2-butoxyethoxy)V methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethyl)
~oxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (addition mol g
2n=6), allyl methacrylate, methacrylic acid dimethylaminoethyl methyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, donylidene chloride, isoprene, chloride, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, vinyl Examples include benzoic acid methyl ester.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibdel itaconate.

- Examples of the maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the fumarated diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethyl acrylamide, dimethylamine ethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.: Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide 7mido, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide , N-(2-acetoacetoxyethyl) methacrylamide, etc.; Allyl compounds, such as allyl acetate, allyl cabroate, allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, Methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc. Vinyl ketones, such as methyl vinyl ketone, phenyl ketone, methoxyethyl vinyl ketone, etc. Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyl oxazolidone, Niglycidyl esters such as N-vinyltriazole and N-vinylpyrrolidone, such as glycidyl acrylate and glycidyl methacrylate; Unsaturated nitriles, such as acrylonitrile and methacrylate trile; and polyfunctional monomers, such as divinylbenzene and methylenebisacrylamide. , ethylene glycol dimethacrylate, etc.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid; Acrylic acid monobutyl etc. ditraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkylsulfonic acid acids, such as niacrylamide alkyl sulfonic acids, such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropylsulfonic acid;
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid: methacrylamide alkylsulfonic acid, e.g. 2-methacrylamido- 2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxypurkyl phosphate, such as acryloyloxyethyl phosphate, 3-acryloyl Oxypropyl-2-phosphate, etc.: Methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Sodium 3-arylokydi-2-hydroxypropanesulfonate, etc., which has two hydrophilic groups. Can be mentioned. These acids may be salts of alkali metals (such as N81) or ammonium ions. Furthermore, other monomer compounds include U.S. Patent No. 3.459.790, U.S. Patent No. 3,438,708, and U.S. Patent No. 3,554.987.
Ji! , No. 4,215,195, No. 4,247,
Crosslinkable monomers described in JP-A-51-205735 and the like can be used.

Examples of such crosslinking monomers include N
-(2-acetoacetoxyethyl)acrylamide, N
-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide and the like can be mentioned.

Among these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.

Next, an example of synthesis of the latex of the present invention will be given.

Below is the margin Synthesis Example 1 360 V of distilled water degassed with N2 gas in a 1i Kolben
12 and synthetic water-soluble polymer (SP-8) 4.5
! ;Add 1 and raise the temperature to 80°C. Distilled water 51
(0.27 g of ammonium peroxide dissolved in 1 was quickly added, and a mixture of 89.1 g of ethyl acrylate and 0.9 g of acrylic acid was added dropwise thereto over about 1 hour. After the dropwise addition was completed, the mixture was further stirred for 4 hours to react. After the reaction, unreacted monomers were collected by steam distillation for 1 hour, cooled to room temperature,
The desired latex A was obtained.

The average particle size of the obtained latex was 0.2μ.

Synthesis Example 2 360vQ of distilled water degassed with N2 gas in 11 Kolben
and synthetic water-soluble polymer (SP-12) 4,5a
and raise the temperature to 80℃. To this, 0.21 g of perfilIil ammonium dissolved in distilled water 5112 was quickly added, and 90 g of ethyl acrylate was added dropwise thereto over about 1 hour, and after the dropwise addition was completed, the mixture was stirred and reacted for an additional 4 hours.

After the reaction is completed, 1tr! Steam distillation was performed for 1 hour to recover unreacted monomers, and the mixture was cooled to room temperature to obtain the desired latex B (19). The average grain size of the obtained latex was 0.1μ.

Synthesis Example 3 360 d of distilled water degassed with N2 gas and 2.3 g of degistran sulfate were placed in a 12-piece Colben and heated to 80°C. To this, 0.27 o of ammonium persulfate dissolved in 5112 distilled water was quickly added, and 41 g of butyl acrylate, 49 g of styrene, 1 acrylic MO,
Add the mixture (h) dropwise over about 1 hour, and after the completion of dropping, add 4 more drops.
Stir for some time and react. After completion of the reaction, unreacted monomers are recovered by steam distillation for 1 hour, and the desired latex C is obtained by cooling to air temperature. Particle size 0.25μ and number average molecular mm
It was n-660,000.

Synthesis Example 4 360 mN of distilled water degassed with N2 gas in 11 full pens
and raise the temperature to 80℃. To this, 0.27 CI of ammonium persulfate dissolved in 5 vQ of distilled water was quickly added, and 40 g of butyl acrylate and 50 g of styrene were added thereto.
The mixture was added dropwise over about 1 hour, and after the addition was completed, the mixture was stirred and reacted for 4 hours. After the reaction is completed, steam distillation is performed for 1 hour to remove unreacted substances. − is collected.

A synthetic water-soluble polymer (SP
-1>! After adding IM and stirring for 2 hours, the mixture was cooled to air temperature to obtain the desired latex D. The average particle size of the obtained latex was 0.3μ.

Synthesis Example 5 Similar to Synthesis Example 1, compound T-1 having a group to which the radical of a hydrophilic group can easily chain transfer instead of the synthetic water-soluble polymer
Latex E was synthesized by adding 0.03 (J).

Synthesis Example 6 Ethyl acrylate of Example 1, synthetic water-soluble polymer (
SP-8> butyl acrylate 89. IQ
The same reaction as in Example 1 was carried out using 5 g of Polymer D-14, which has a double bond in the main chain, to obtain the desired latex. The number average molecular fi1Mn was 760.000, and the average particle size was 0.28μ.

Next, the polymer hardener used in the present invention will be explained.

The polymer hardener used in the present invention refers to poly7- having a functional group capable of crosslinking with gelatin and a polymer having a functional group capable of crosslinking with gelatin via the hardener. The former polymers also include modified gelatin, which is obtained by weakly reacting gelatin with a small amount of a hardening agent.

These polymeric hardeners are disclosed, for example, in Unopened Patent No. 3.057.
, No. 723, No. 3,671,256, No. 3,39
No. 6,029, No. 4,161,407, No. 4,207
, No. 109, British Patent No. 1,322,971, Japanese Patent Publication No. 17112-1971, Japanese Patent Publication No. 94817-1987, Japanese Patent Publication No. 51-94817
B-66841, No. 57-207243, No. 5
Patents such as 9-121327@ and "The Theory of the Photographic Process" 4th edition (T, H.

James et al.) page 94, “Polymeric Amine
and ammonium ruts (E, J, Goethals et al.)
321 pages, etc., can be used.

Among these polymer hardeners, preferred are modified polysaccharides such as dialdehyde starch, modified gelatin with pendant gelatin crosslinking agents, water-soluble polymers grafted with functional groups capable of crosslinking with gelatin, Examples include polymers or copolymers of vinyl monomers having functional groups capable of crosslinking with gelatin.

Particularly preferred are polymers or copolymers of vinyl monomers having functional groups capable of crosslinking with gelatin.

Polymers or copolymers made of vinyl monomers having functional groups capable of crosslinking with gelatin include the following general formula [I
], [Ir], and 'I[l] are preferred.

Below is the margin General formula [11 R1 % Formula % General formula ■ General formula [11 % Formula % Here R1 is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 lower alkyl groups, Q represents a sign -CO-1-CO2-1-CON- (R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an alkylene group, or a group having 6 to 12 carbon atoms; represents an arylene group having carbon atoms of -1 represents a divalent group having 1 to 12 carbon atoms and including at least one bond. G represents a group involved in a crosslinking reaction with gelatin. M represents an alkali metal, and ■ and n each represent 0 or 1 (provided that m+n≧1). h represents O or 1.

○ includes, for example, the following groups.

C) 13 -COz-, -CONH-, -CON-.

Margin below This includes, for example, the following groups:

-C142CO2CH2- -CH2CO2CH2CH2- -CH2C)12CO□CH2C)(2--fCH2→
s CO2CH2C)l 2-+CH2-+qCO2C
H2C) 12--CH2NHCOCH2- -CH2NHCOCH2CH2 ÷CH2yaNHCOCH2CH2- +CH2+TN HCOCHz CH2--fCH2+
PossibleNHCOCH2CH2--CH20CH2--CH20)-120C)(2C)(2C)12--+
qt-M2L;)-12-, -CH2NCH2C)12
--COC82C)42- -C)lzCOCHzC)-12- -8OCH2C)12- -C'82SOC)+2C)J2- -5O2CH2C)-12- -8,02CHzCHzSO2CHzeH2--8O2
CHzCH2SO2CH2CHCH2-H -8O3CH2CH2CH2- -9O:+CHzCO2CHzC)4z--QO3CH
2CH2CO2CH2CH2--802NHC)-+2
CO2CH2CH2--8O2NHCH2CHxCO2
CH2CH2--NHCONHCH2CHz- -C)IzN)ICONHCH2CHz--NI-IC
O2CH2CH2- -CHzN, HCO2CHzCH2- -CONHCH2+, -CONHCH2C)+2+.

-CONHCH2CH1C) (2-.

-CONHCH2CHzCH2CHxCH2-.

-COCHzCI-120c:0CHzC)+2-.

-CONHCH2CONHCH2-.

-CON)JC)12cONHcH2cON)+2cH
2-.

G includes, for example, the following groups.

-CH2=CH2, -CH2CH, C1, -CH2S
O2N a , N HCH2P O(ON a
)2, N (CH3)2, -〇NH4, -0CH,
, N HS Ox N a , CH2CH2B
r.

-CH2-CH202CCHC12 0 magazine -CO20H2CN -0O2CH2CO
zC2Hs-CO2CH2CONH2-CH2CH2C
QC)l:1-COzN=CI-1cHa-
CO2N=CCCHB)2-CO2CH2CH2Br
-CO2CH2CH2CCH3 The polymer hardener according to the present invention has the general formula [I], [11,
It may be a so-called homopolymer consisting only of the repeating 11/ represented by [[[ ], or it may be a so-called copolymer with other comonomers that can be co-laminated. The material used in the reaction may be monounsaturated ethylene compounds or diolefin compounds. For example, acrylic acid and its esters, methacrylic acid and its esters, Acids and their esters, vinyl esters, maleic acid and their diesters, fumaric acid and its diesters, itaconic acid and its diesters, olebuins, styrenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers , vinyl ketones, polyfunctional monomers, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, and the like.

To give specific examples of these polymerizable unsaturated compounds, examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert
-Octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoedyl acrylate, 2-acetoxyethyl acrylate, dimebyl aminoedyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclo hexyl acrylate, cyclohexyl acrylate, furfuryl acrylate,
Tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxy pendel acrylate, 2.2
-dimethyl-3-hydroxypropyl acrylate, 2
-Methoxyethyl acrylate, 3-methoxyethyl acrylate, 2-ethoxyethyl acrylate-1, 2-
iso-propo-4 diacrylate-1-12-butyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-<2-butoxyethoxy)ethyl acrylate, θ)-methoxypolyethylene glycol acrylate (addition mole number n=9>, 1-proE-
2-methoxyethyl acrylate, 1,1-dichloro-
Examples include 2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, amino methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N
-ethyl-N-phenylaminoethyl methacrylate,
2-(3-phenylpropyloxy)ethyl methacrylate, dimeb-ruaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl Methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-
Methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate-1, 2-iso-proboxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy) ) Ethyl methacrylate, 2-(2-butoxyethoxy) nibble methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles n==6), and the like.

Examples of vinylnisdels include vinyl acetate, vinyl p[1 pianate, vinyl buglate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl allotate, vinyl benzoate, salidylic acid. Examples include vinyl.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimedylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, promstyrene, and vinylbenzoic acid methyl ester. It will be done.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimebble fumarate, and dibutyl fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, human[1-xymethylacrylamide, methyl-xyethyl acrylamide, dimethylamineethylacrylamide, phenyl Examples include acrylamide, diethylacrylamide, diethylacrylamide, β-cyanoethyacrylamide, N-(2-ace1-al-xynyl)acrylamide, and the like.

Examples of methacrylamide include methacrylamide, methylacrylamide, ethylmethacrylamide, propylacrylamide, butylmethacrylamide, and tert-
Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methyl methacrylamide,
Dimethylamine ethyl acrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanethyl methacrylamide, N
-(2-acedo-ethoxyethyl)methacrylamide and the like.

Examples of allyl compounds include allyl acetate, allyl caproate, allyl laurate, and allyl benzoate.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like.

Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, and methoxyethyl vinyl ketone.

Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, and N-vinylpyrrolidone.

Examples of glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylate trile.

Examples of polyfunctional monomers include divinylbenzene, methylene bisacrylamide, and ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, itaconic acid (noalkyl, e.g. monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleate, e.g. monomethyl maleate, mononibble maleate, maleic acid) Monomethyl acids such as ditraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxynibble sulfone, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkyl sulfone Acids, such as methacryloyloxyalkylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc. Niacrylamidoalkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid acids, such as 2-methacrylamido-2-methylbutanesulfonic acid; methacrylamide alkylsulfonic acids, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, etc. -methacryloyloxyalkyl phosphates such as methacrylamide-2-methylbutanesulfonic acid, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.: methacryloyloxyalkyl phosphates, such as methacryloyloxyebul phosphate, 3- Examples include methacryloyloxypropyl-2-phosphate; sodium 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups; etc. These acids are salts of alkali metals (e.g. Na SK) or ammonium ions. Other polymerizable unsaturated compounds include those described in U.S. Patent Nos. 3,459 and 7.
No. 90, No. 3.438.7oa@, No. 3,554,
No. 987, No. 4,215,195, No. 4,247
, No. 673, JP-A No. 57-205735, and the like can be used. Examples of such crosslinking materials include N-(2-acetoacetoxyethyl)acrylamide,
N-(2-(2-acetoacetoxyethoxy)ethyl)
Examples include acrylamide.

Next, specific examples of the polymer hardener according to the present invention will be shown, but the present invention is not limited thereto.

Margin below Air- 〇 0.

Q O00ri
111] >
Therefore, the latex and polymer hardener on the surface of which a hydrophilic group is fixed according to the present invention are contained in photographic constituent layers such as a protective layer, a silver halide emulsion layer, and an intermediate layer. The effects of the present invention, especially when the hardening agent is contained in the same photographic constituent layer, or the latex is contained in one of the adjacent photographic constituent layers and the polymer hardener is contained in the other, the trailing failure is significantly improved. .

In the present invention, the amount of latex used is 20% or more and 300% or less, preferably 50% by weight based on gelatin.
% or more and 200% or less. If the amount of latex used is too small, dimensional stability will be poor, and if it is too large, sufficient film strength will not be obtained.

Further, the polymer hardening agent used in the present invention has a weight ratio of 0.1% to 30%, preferably 0.5% to gelatin.
% or more and 15% or less. If the amount of polymeric hardener is too small, sufficient hardness cannot be obtained, and if it is too large, problems arise in coating properties.

As a binder for the photographic constituent layer, gelatin or gelatin MS may be used in combination with the latex according to the present invention on which the hydrophilic groups are fixed on the surface.

In addition to lime-treated gelatin, gelatin
of the society of science
Photography of Japan (Bull, 3o
c, 5ciShot, Japan, )No,
16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include various compounds such as acid halides, Mfi hydrates, isocyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used. Specific examples thereof include U.S. Patent Nos. 2,614,928 and 3,132,945.
No. 3,186.846, British Patent No. 3,312,553, British Patent No. 861,414, British Patent No. 1.033.189, British Patent No. 1,005,784, Japanese Patent Publication No. 42-26845, etc. has been done.

The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

Furthermore, the silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. It may be a particle in which an image is mainly formed on the surface, or it may be a particle in which an image is mainly formed inside the particle.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical or plate shape. It may also have a crystalline form.

In these particles, any ratio of the (100) plane to the (1117 plane) can be used. Also, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, and particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a member metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

Further, the silver halide emulsion layer may contain a dye-forming coupler to produce a color light-sensitive material.

[Examples of the Invention] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A silver chlorideodobromide gelatin emulsion containing 75 mol % silver chloride, 25 mol % silver bromide, and 1 mol % silver iodide was added with o, eg 4=hydroxy-6 per mol silver halide. - adding methyl-1,3,3a,7-chitrazaindene,
The dry weight of the latex of the present invention is 1. OQ was added, and depending on the sample, a polymer hardener was added in an amount of 0.1/f, and the material was placed on an undercoated polyethylene terephthalate support.
The first layer was applied so that silver m was 4.0 g/v2.

Furthermore, on top of this silver halide emulsion diagram, as a second layer, the total solid content of gelatin and latex is 1.50/”
I', Mucok D-ruic acid 0,05 (1/'''
, depending on the experiment, the polymeric hardener may be added to 0. IQ/'t"
A silver halide photographic light-sensitive material was obtained by coating and avoiding drying.

The types of latex and polymer hardener used are shown in the table.

・ Synthesis method of latex for comparison Synthesis Example 1 A 1000 d four-bottle flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and a 350 d pure water
Add cc and heat until the internal temperature reaches 80°C. During this time, nitrogen gas was added to the groove, and after the internal temperature reached 80°C, nitrogen gas was passed for another 30 minutes. .

Add 4.5 g of sodium dodecylbenzenesulfonate, then add 0.4 g of ammonium persulfate as an initiator.
A solution of 5 g dissolved in 10 cc of water is added, and then a mixture of 90 g of ethyl acrylate is added dropwise using a dropping funnel over about 1 hour. Five hours after the addition of the initiator, the mixture was cooled, adjusted to pH 6 with aqueous ammonia, and filtered to remove dust and coarse particles to obtain a comparative latex liquid (a).
~ Synthesis Example 2 Butyl acrylate 39. as a polymerizable unsaturated compound.
5 (1) Synthesized in the same manner as in Production Example 1 except that a mixture of 49.5 g of styrene and 1 g of acrylic acid was used to obtain a comparative latex liquid (b).

The resulting samples were visually observed for the occurrence of trailing failures during coating, and further, each sample was exposed to wedge light and subjected to the following treatments to examine its dimensional stability. The results are shown in the table.

[Dimensional Stability] Dimensional stability accompanying development processing was determined from the dimensional change rate measured using a bottle gauge. Assuming that the dimension of an exposed sample having a length of 200III11 before processing is X mm and the dimension after development processing is Y mm, the dimensional change rate is determined by the following equation.

Dimensional change rate (%) = ((Y X) / 200)
x 100 In the industry, it is considered that there is no practical problem if the dimensional change rate is ±0.01% or less.

[Tailing failure 1 Samples with no tailing that starts to pull in the application direction are A, samples with 1 or 2 occurrences in 1:+' are B,
Anything higher than that was rated C.

[Processing conditions] Development: 29°C, 30 seconds Fixation: 28°C, 20
Wash with water for seconds 20℃ 2
Dry for 0 seconds at 45℃ 3
0 seconds [Developer (undiluted solution)] Potassium bromide 2.5 g Disodium ethylenediaminetetraacetate 1Q Potassium sulfite (
55% aqueous solution) 901g potassium carbonate
25g hydroquinone
101J5-Methylbenzotriazole 100
mg5-nitrobenzotriazole 100mg1
-Phenyl-5-mercaptotetrazole 30mQ5-nitroindazole 50mg1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.50 diethylene glycol 60Ω sodium hydroxide Add enough water to adjust the pH to 10.6 50
Finish to 0-. (pH 10,6) When used, the above stock solution is diluted with water to double the volume.

[Fixer J (Part A) Ammonium thiosulfate 170g Sodium sulfite 150 Sodium borate 6.5g Glacial acetic acid
12d Sodium citrate (dihydrate)
Add 2.5 g water to make 275d.

(Part B) Aluminum sulfate (18 water points) 15g 98% sulfuric acid Add 2.5g water to make 40vQ.

The method for preparing the liquid used is to add approximately 60% water to the above Bart A275-.
After adding 0 Dai, add Bart 840 V (l), and then add water to make + OOOd.

As can be seen from the margin table below, when a polymer refinishing agent and the latex of the present invention are combined, whether they are in the same layer or in separate layers, trailing problems occur. did not occur at all. Moreover, the dimensional stability of these samples was very good.

However, when a polymeric hardener and a comparative latex are combined, they are not only present in the same layer, but also next to each other. Trailing failures occurred even in the upper layer.

When the latex of the present invention is used in photosensitive materials using polymer hardeners, no trailing failure occurs for the first time.
A silver halide photographic material with good dimensional stability could be obtained.

Claims (1)

[Claims] A silver halide photographic light-sensitive material characterized in that a photographic constituent layer on a support contains a latex having a hydrophilic group fixed to the surface and a polymer hardener.